Anti-static high molecular weight compounds



United States Patent Ofiice Patented Dec. 21, 1965 3 Claims. or. 106-477) The present invention relates to a process for the antistatic finishing of high molecular weight compounds.

Shaped articles of any kind of high molecular weight materials, for example synthetic plastics, have a tendency towards electrostatic charging particularly when the material used possesses very good electric properties. Owing to this electrostatic charging these shaped articles, when used in practice, already exhibit dust deposits at the surface after a short time which deposits, in the case of a strong electrostatic charging, show the well-known zigzag design or crows feet. Owing to this strong electrostatic charging, moreover, sparking may occur on account of the great potential dilference.

In the case of fibers or fabrics the static charge manifests itself by rapid and strong dirtying of said fibers or fabrics. Owing to these disadvantages of the static charge, the use of such polymers may become uninterestmg.

Many processes are known according to which electrostatic charging can be prevented or at least diminished. Thus it has been known for a long time, for example, to condition shaped articles after their fabrication, i.e. to expose them to moist air. Injection-molded pieces or fibers, for example of polyamide, cellulose acetate or viscose that are to be rendered resistant to electro-static charge, absorb water to a certain extent by this treatment whereby the electric conductivity is strongly increased.

Apart from the fact that some plastics, for example polyolefins, practically absorb no water and the shaped articles of this material cannot be rendered resistant to electrostatic charge in such a manner, this method also has the disadvantage that the water content of the plastics articles is reversible, i.e. the anti-static effect is lost when storing the articles treated in this manner in a dry atmosphere.

Since it is in most cases not sufficient to expose the shaped articles to moist air in order to obtain an antistatic eifect, various processes have been developed in which the plastics material or the surface of the shaped articles made therefrom is modified by means of antistatic agents in such a manner that the static charge is diminished. Quite a number of compounds have been proposed for this purpose; These compounds can be classified in the following five groups:

(1) Nitrogen-containing compounds such as amines,

amides and quaternary ammonium salts,

(2) Sulfonic acids and aryl-alkyl-sulfonates,

(3) Phosphoric acids and aryl-alkyl phosphates, as well as phosphoric acid ester amides,

(4) Polyglycols and the derivatives thereof including polyglycol esters of fatty acids as Well as polyglycol aryl alkyl ethers,

(5) Polymers of multivalent alcohols and the derivatives thereof.

The anti-static agents can, depending on the kind of agent, either be applied to the shaped article made of plastics materials by treating them with a solution of said agents, or they may be incorporated by admixing the respective agents to the plastics powder prior to its processing.

It is also known to incorporate strongly hygroscopic inorganic salts but this is not generally done on account of the risk connected therewith of corrosion occurring on the processing machines.

The subsequent treatment of shaped articles of plastics materials with solutions having an anti-static effect has serious drawbacks:

The anti-static effect generally depends on the content of Water vapor of the atmosphere. The adhesion of the subsequently applied compounds is insutficient in the case of the compounds known hitherto so that they are effective during a limited period only on account of abrasion and when being used everyday. Moreover, the danger exists that the surface of the material is changed. Some of the anti-static agents to be applied are exceedingly hygroscopic so that they absorb an unnecessarily large amount of water. They are, moreover, in most cases not harmless from a physiological point of view.

An anti-static treatment by incorporating the anti-static agents has the advantage that it is possible at any time to finish high molecular weight materials on demand With anti-static agents also after their polymerization. In order to attain a sufficient anti-static effect the already known organic compounds that are capable of being incorporated must, however, be added in amounts which entail a modification of the characteristic properties of the plastics material such, for example, as: a decrease of the temperature ranges suitable for the processing, a reduction of the hardness, the rigidity, the thermostability under load, a deterioration of the color, etc. In many cases the compounds concerned are agents by whose incorporation the high molecular weight material finished therewith loses its physiological harmlessness.

Really effective anti-static agents that can be applied on an industrial scale for the incorporation in synthetic plastics are not known hitherto.

Another possibility of rendering high molecular weight materials resistant to electro-static charge consists in incorporating additives during the polymerization. This method has the disadvantage that the high molecular weight material is finished by means of anti-static agents already in the manufacturing process, while the fabricator can in many cases decide only shortly before the final shaping whether an anti-static finishing is required for the desired purpose, or whether the slight deterioration of the electrical properties connected therewith is unwelcome. Moreover, by adding the hitherto known additives during the polymerization the characteristic properties of the materials, for example the absorption of water, the chemical resistance, toughness and hardness are modified in many cases.

Now we have found that for the antistatic finishing of organic high molecular weight compounds there may be used as anti-static agents organic phosphorus amides of the general formula R2 or the respective ammonium salts or R Z:Y while the two radicals need not be equal; R represents -H M alkyl, preferably methyl; R represents l erably alkyl (containing 1 to carbon atoms), but it may also mean cycloalkyl, aryl or alkylaryl.

When R and R represent hydrocarbon radicals, they may also be substituted. As substituents there enter into consideration, for example: halogen, amino groups, substituted amino groups, oxy groups, alkoxy groups, thio ether, mercaptane groups, sulfonamide groups, carboxy alkyl groups, aromatic and heterocyclic substituents.

The concentration of the phosphorus compounds in the plastics material may advantageously amount to 0.1 to 7% by weight, preferably 0.5 to 4% by weight. Smaller amounts may also be sufiicient.

Phosphorus amides in which R and R represent aliphatic radicals or H generally have the best anti-static effect above all in those cases in which R represents a methyl group and R a longer alkyl radical such as, for example, the stearyl or dodecyl radical, and X or Y represent alkyl radicals or amines substituted with alkyl radicals. As such compounds there are mentioned, for example, phosphorus acid-N-methylstearylarnide-diamide. Compounds with aromatic or cycloaliphatic hydrocarbon radicals partially exhibit a lower efficacy. As shown in Example 8, compounds containing aromatic substituents may also be excellent anti-static agents. Whether the efficacy of these compounds depends on the fact that at the high working temperatures a splitting off of the aromatic residues takes place and a phosphorus amide which is free from aromatic groups then acts as an antistatic agent in the final product, or whether the compounds in themselves are effective, does not play a decisive role for the desired improving effect.

As suitable anti-static agents there may, for example, be used the following compounds, without limiting the process to these compounds:

Phosphoric acid-N-methylstearylamide-diamide, phosphoric acid-tri-N-dimethylamide, phosphoric acid tridodecylamide, phosphoric acid tristearylamide, phosphoric acid dibutylamide-diamide, phosphoric acid dodecylamide-diamide, nonylphosphonic acid methylstearylamide-amide, octylphosphonic acid-distearylamide, and octylphosphonous acid-N-methylstearylamide.

It is a special advantage of the present invention that quite a category of compounds are described as anti-static agents so that of the great number of effective products there may, according to requirements, be chosen compounds particularly suited for a certain synthetic plastic or for a special field of application. According to the special requirements of the services there may be chosen compounds which, on account of their solubility in water or organic solvents or in the synthetic plastic itself, or owing to their color decomposition, melting or boiling temperature, etc., yield final products having optimum properties. In many cases it may also be advantageous to use mixtures of two or several of the phosphorus amides mentioned above.

For the industrial utilization of a product the manufacturing process and, connected therewith, the economy of the process plays a decisive role. From the great range of the anti-static phosphorus amides that may be used it is easy to choose products that fulfill the requirements with regard to economy.

In German patent application as laid open to public inspection No. 1,091,078 there is described the subsequent anti-static finishing of filaments and sheets with solutions of phosphoric acid ester amides. As compared with that application the present invention has considerable advantages. Thus the subsequent anti-static finishing with phosphoric acid ester amides displays the disadvantages mentioned above. In the subsequent application of the antistatic agents it is only attempted to finish the surface of the plastics parts in such a manner that the electrostatic charge can flow off by reducing the surface resistivity.

' Inthe present invention, however, the transmission resistivity is decreased by the incorporation of the compounds enumeqed.

The transport of electrical charge is dependent in a much higher degree on the transmission resistivity, so that in this manner static charging is not only avoided permanently but also the charge is no longer primarily influenced by the moisture content of the surroundings.

When adding small amounts of the cited compounds to the plastics materials an anti-static effect is already achieved so that shaped articles made from such mixtures no longer charge at the surface and no longer exhibit a tendency towards attracting dust. The mechanical and thermal properties, the thermostability under load as well as the color and transparency of the polymers remain practically unaltered by an addition of the said compounds while the fastness to light is partially even improved.

The working conditions and the range of temperature in which the synthetic plastics can be shaped by a thermoplastic process remain the same. Moreover, the products are for the greater part odorless and well compatible with all polymers. Furthermore, the greater part of the compounds described is physiologically harmless; for example in the case of the phosphoric acid-N-methylstearylamide diamide the test as to acute toxicity showed a value of LD :10 g./kg. The anti-static effect attainable is independent of the moisture of the surroundings and of a practically unlimited duration. The surface does not become hydroscopic but remains unchanged. Some of the electric properties of the polymers are influenced by the addition of the anti-static agents for this constitutes their anti-static efiicacy. The deterioration of the specific transmission, and, in some cases, also of the surface resistivity as well as the dielectric properties is so trifling that in most cases it is of no importance even for the application of the polymers in the field of electrical engineering.

By adding compounds of the category as described above all high molecular weight materials can be improved that have the tendency of getting dirty by at tracting dust owing to electrostatic charging. These compounds exhibit a particularly good efficacy, for example, in polystyrene and in the copolymers of styrene with butadiene and/or acrylonitrile and/or vinyl .carbazole, in polyvinyl chloride and vinyl chloride copolymers, polyterephthalates, polyolefins, such as the polymers and copolymers of ethylene, propylene, butene-(l), pentene-( 1), 4-methyl-pentene- 1 hexene-( 1) 5,5 -dimethyl-hexene- (1), octadecene-(l), 4-phenylbutene-(1) as well as vinylcyclohexene, polycarbonates, polyacrylonitrile, polyacrylic acid esters, polymethacrylic acid esters, polyamides, polyurethanes, polyvinyl esters, polyacetals, polymers of fiuorolefins, cellulose derivatives and polymer mixtures containing the enumerated polymers. Also unsaturated polyesters and epoxy resins hardened with reagents having a basic character as well as raw materials for lacquers can without difficulties acquire an anti-static finishing prior to or during their processing by an addition of the compounds cited. However, when processing the polyester resins it may, after the addition of the anti-static agents, become necessary to carry out the operation with hardening/ accelerating systems differing from those usually employed. The compounds of the said category can be added prior to or during the polymerization, and also later on to the pulverulent high molecular weight polymer as well as to the granular product. Depending on the nature of the synthetic plastics the com pounds can be admixed in the melt, in solution and by application to the pulverulent or granular high molecular weight polymer. The admixture is most advantageously effected prior to or during the processing. It was found that the. technique of incorporation is of little importance. It is important, however, that the anti-static agents are distributed in the synthetic plastic as evenly as possible. Application during the polymerization is also possible.

The high molecular weight polymers provided with an anti-static finishing can be processed by all customary processing methods, for example on molding presses, in-

fibers, filaments, monofilaments, etc. The resins admixed 5 with the compounds mentioned above can be processed in the usual manner as resin varnish or casting resin or in combination with glass fibers and/ or fillers.

The high molecular weight polymers finished in this manner are especially interesting for packaging purposes 10 (packing-material, canisters, bottles, beakers), as accessories for vacuum-cleaners, band-conveyors, showroom patterns and masters, parts for casings (for example for radio and television sets, vacuum cleaners), electric installations such as lighting fixtures, cable insulations, 15

plugs, switches or armatures, air conditioning and ventilating equipments, plastics table ware, kitchen machinery, filaments, fibers, fabrics, sheets, lacquers, that is to say in all those cases in which an anti-static finishing is required. 20

The anti-static effect of inorganic or organic compounds in high molecular weight materials can be determined most easily by means of cigarette ash. For testing these materials plates obtained by extrusion, injectionor com 6 pression-molding are vigorously rubbed with a woolen cloth for about 15 seconds and held about 2 mm. above powdery cigar or cigarette ash. When the extruded or molded plates have good anti-static properties, they do not attract cigarette ash.

Another method for determining the electrostatic charge consists in measuring the specific transmission resistivity. An attraction of cigarette ash was no longer observed when the transmission resistivity had a value of about 10 ohms/cm. Quite a number of further methods are known for determining the electrostatic charge, but it was found that only the two test methods mentioned above furnish genuine values which approach those found in practice.

The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by Weight:

EXAMPLES Several anti-static compounds corresponding to the summation formula explained in the description were incorporated in various high molecular weight polymers. The anti-static agents used in Examples 1 to 13, the amounts added thereof and the test results are listed in Table 1.

TABLE 1 Transmis- Transmis sion resion re- Ex. Thermosetting or therrnosistivity Addition sistivity Attrac- No. plastic high molecular ofthe Anti-static agent Formula percent after the tion oi weight compound plastics addition ash material ohms/em. ohms/em.

II/ 1 Polystyrene 10 Octylphosphonous ac1d-N- CsH11-PH 0 1111 1 1- 10 3 methylstearylarnide.

N CisHm 2 Acrylonitrile/styrene 10 Phosphoric aeid-tristearyl- O=INHC H 1 1-10 copolymer. amide.

NHClKHIiT NHC12 2s 3 Butadiene/styrene 10 Phosphoric acid dedecyl- O=P-NH2 0,5 1.1012

eopolymer. amide-diamide.

CH O I ll is sv 4 Polyglycolterephthalate. 10 Octylphosphonlcacld-di- CBH17P 1.5

(stearyl-meth ylamide) 0 H3 CISH37 /CH N\ C12H25 5 Branched(high-pressure)- 10 Phosphoric ac1d-methyl- O=PNH2 1.5 1-1014 polyethylene. dodecylarnide'diamide.

NHz

6 Linear (low-pressure)- 10 Phosphoric aeid-tri-N di- O=PN(OH3)2 1 1-10 polyethylene. methylamide.

NH-C H 7 Polypropylene 10 PhOSPIOIlO acid-triethyl- O=INHC2H5 0.75 1-1011 arm e.

NIP-C 13 Q) 8 Polybutene-l 10 Phosphoric aeid-N-methyl- O=PNH- 1,0 1. 1s stearylamide-dianilide.

NHOH3C H 7 Footnote at end of table.

TABIJE =1Continued Transmis- Transmission resion re- Ex. Thermosetting or therrnosistivity Addltion sistivity Attrac- N 0. plastic high molecular of the Anti-static agent Formula percent after the tion weight compound plastics addition ash material ohms/em. ohms/cm.

NH C12H25 9 Polyvinyl chloride with 10 Phosphoric acid-tridodeeyl- O=PNHC12Hz 1. 1-10 dioctyl phthalate. amide.

NH C 12 25 011 N 10 Polycarbonate 10 Oetylphosphonic acid- CSH11P 0181131 1. 0 1-10 stearylmethyl-amide-amide.

O N H2 /OH 1l Epoxido resin (hardened 10 Thiophosphoric acid-methyl- S=P-NHCH 0 75 1.1013

with reagents having a octylamide-di-(methyl basic character). amide).

N H CH 12.-." Polyester resin as glass 10 Thiophosphorio aeid-N- S =PNH Q 5 1.1013

fiber laminate or as methyl-stearylamidelacquer coat. diamide.

NHZ

13 Polypropylene 10 N-methylstearylamide- PNH 1. 0 1.1013

* =No attraction of ash. +=Attracti0n of ash.

The specific transmission resistivity of the injection- E l 6 molded plates was measured according to DIN (German Industrial Standards) 53482 and the tendency of said plates to attract cigarette ash was tested by rubbing them with a woolen cloth.

The anti-static agents were incorporated in the following manner:

Examples 1, 5, 8 and 13 10 kilos each of the respective plastics material were mixed with the indicated amounts of the anti-static agents on an impeller, extruded into bands, worked up into granules and injection-molded into 1 mm. thick plates.

Examples 2, 3 and 10 The indicated amounts of the anti-static agent were applied in a puverulent state to 10 kilos of the indicated plastics granular product according to the dry dyeing process. A roller vat was used as a means for applying the anti-static agent. The material treated in this manner was then extruded, worked up into granules and injection-molded into 1 mm. thick plates.

Example 4 Octyl phosphonic acid di-(stearylmethylarnide) in the form of a 10% methanolic solution was added to poly ethylene glycol'terephthalate. After evaporation of the solvent and drying of the mixture, the material was spun in the usual manner.

In a mixer 75 grams of liquid phosphoric acid tri-N- dimethylamide were introduced through nozzles into 10 kilos of linear (low-pressure) polyethylene powder. After thorough homogenizing the mixture was worked up into granules which were injection-molded into plates.

Example 7 10 kilos of polypropylene powder were mixed in a mixer with 750 grams of a hot 10% solution of phosphoric acid triethylamide in ethanol. After evaporation of the solvent at C., the mixture was Worked up into granules which were injection-molded into plates.

Example 9 200 grams of a commercial epoxy resin on the basis of 4,4-diphenylol propane-l-epichlorhydrine having an epoxide equivalent of were mixed with 16 grams of diethylene triamine and 7.5 grams of a 20% solution of thiophosphoric acid methyloctylamide di-(rnethylamide) in dibutyl phthalate. The mixture was cast into a plate and hardened at room temperature.

Example 12 10 ished with 75 grams of phosphoric acid-N-methylstearylamide-diamide in the same manner as described in Example 16 in order to acquire anti-static properties, and the material was injection'molded into plates.

200 grams of a commercial unsaturated polyester resin The plates had a specific transmission resistivity of which was obtained by condensation of 5 moles of ethyl- Ohms/cm. After being vigorously rubbed with a woolen ene glycol with 3 moles of maleic anhydride and 2 moles cloth the plates did not attract cigarette ash. of phthalic anhydride and final dissolution of the condensation product in 30% by weight of styrene, was cast Example 18 into plates after the addition of 2% of methyl ethyl 10 As described in Example 16, 75 grams of phosphoric ketone peroxide, 0.1% of cobaltous naphthenate as well acid-N-methylstearylamide-diamide were added to 10 as 0.5% of thiophosphoric acid-N-methylstearylamidekilos of a commercial copolymer of styrene and butadiene diamide and hardened at room temperature with the ex- (density: 1.06, Martens temperature 68 C., specific clusion of air. transmission resistivity l0 ohms/cm.) and injection- Table l which lists the test results shows that an excelmolded into plates. lent anti-static effect can be attained with all of the com- The plates had a specific transmission resistivity of pounds enumerated. 10 ohms/cm. After being vigorously rubbed with a Example 14 woolen cloth the plates did not attract cigarette ash.

10 kilos of isotactic polypropylene (density 0.905) E l 19 were mixed, respectively, with varying amounts of phosf 1 phoric acid-N-methylstearylamide-diamide on an impeller, m 05 o a granu l mlxture of S.tyren/acry1mtn1e extruded into bands, worked up into granules which were cimfflymer and a butadlene/acrylommla 1 (diminjection-molded into 1 mm. thick plates. The specific slty' 1 l Martens timperamre 70 syieclfic transmission resistivity of these plates was measured ac- P F were f cording to DIN (German Industrial Standards) 53482. aimdlcated ExamPlem, W 75 grams of PhOSPhOTIC AS Shown in Table 2, the degree of the antistatic (affect acid-N-methylstearylam1de-diam1de to acquire anti-static depends on the amount of the phosphoric acid-N-methyl- Propertles, and 1116 material Was i n-In ded into stearylarnide-diamide added (cf. the values of the specific P transmissionresistivity). The injection-molded plates had a specific resistivity TABLE 2 Addition of phosphoric acid- N -me thyistearyl-amidediamide in percent 0 0.25 0. 5 O. 75 1.0 1. 5 4. 0 10 Specific transmission resistivity in ohms/cm. (DIN Attraction of cigarette ash after rubbing the plates with a woolen cloth Strong. Little. Verylittle. 4N0 attraction.

Example 15 4 0f 10 ohms/ cm. An attraction of cigarette ash was not Pulverulent isotactic polypropylene (density 0.905) a obsfrveiheven i fi plams had been rubbed vlgor' was mixed on an impeller with 0.5% of phosphoric-acid- Ous y W1 a C of N methylstearylamide diamide, extruded into bands, Example 20 worked up into granules and injection-molded into 1 mm. 200 rams of 01 Vin 1 chloride Owder K value 69 thick Plates: The Specific fj i fi f were mixed with 4 grariis of dibuts l-tin-bis (thioglycoliz: d a y s sll r i i n iii i s t a ir $60 72 0 f rel tiil e m di s tirre acldmctyiestter) and? grams of Phosphoric acid-N meth at 20% C as well as after 5 days storage in the desicylsifj-a-rylamldeidlanilde dlssolved IDA-grams of an epmiy staollrzer. This mixture was plasticized on a roll mill cator. This test shows that the degree of the anti-static and then compression molded into a 1 mm thick plate effect is independent of the moisture content of the sur- While a Comparative plate Without addition S roundmgsphosphoric acid-N-methylstearylamide-diamide attracted Example 16 cigarette ash after being vigorously rubbed with a woolen 75 grams of phosphoric acid-N-methylstearylamidecloth, the plate obtained as described in this example did diamide (melting point l06108 C.) were applied in not attract Cigarette the form of a powder according to the dry dyeing process Ewmple 21 to 10 kilos of polystyrene granules (density: 1.05 g./crn.

Martens temperature 69 C., specific transmission resis- 200 gram? of P y chloride Powder (K tivity 10 ohms/cm). A roller vat served as a means were StITTPd Into 20 g s f a 10% solution of for applying the anti static agent The material thus phosphoric acid-N-rnethylstearylamide-diarnide in ethatained was then extruded, worked up into granules and G5 the Solvent Was evaporated at After injectiommolded into 1 mm thick plates. addition of 4 grams of dibutyl-tin-bis-(thioglycolioacid- The specific transmission resistivity of the polystyrene octyleter) and 4 Q P an epoxide Tfisill as Stabililfif plates finished with an antistatic agent was 10 ohms/ cm. i mixture W Plastlclzed on a T011 mill and p After the plates had been rubbed vigorously with a slon'lQolded mto a thick P woolen cloth they did not attract Cigarette h 70 While a comparative plate without the addition of phosphoric acid-N-rnethylstearylamide-diamide attracted Example 17 cigarette ash after being vigorously rubbed with a woolen 10 kilos of a granular styrene-acrylonitrile copolymer cloth, the plate finished with an anti-static agent did not (density: 1.08 g./cm. Marten temperature C., exhibit a charge that could be measured with cigarette 75 ash.

specific transmission resistivity 10 ohms/cm.) were fin- 1 1 Example 22 In a pilot-plant a solution of polyacrylonitrile (K-value 87) in dimethyl formamide with an addition of 2% of phosphoric acid-N-methylstearylamide-diamide was spun in the usual manner.

Even when the monofilaments which had been wound on a bobbin were rubbed vigorously, said monofilaments did not attract cigarette ash.

Example 23 1.5% of phosphoric acid-N-methylstearylamide-diamide in the form of a 10% methanolie solution were added to polyethylene glycol terephthalate (specific viscosity: 800). After evaporation of the solvent and drying of the mixture the material was spun in the usual manner. The fibers obtained in this manner did not exhibit a static charge that could be detected by means of cigarette ash.

Example 24 10 kilos of linear (low-pressure) polyethylene powder (density: 0.96 g./cc., specific transmission resistivity 10 ohms/cm), were, as described in Example 14, finished with 75 grams of phosphoric acid-N-methylstearylamidediamide in order to acquire antistatic properties.

The specific transmission resistivity of the injectionmolded plates finished in this manner was 10 ohms/ cm. When tested the plates did not attract cigarette ash.

Example 25 10 kilos of linear (low-pressure) polyethylene powder (density: 0.96 g./cc., specific transmission resistivity 10 ohms/cm.) were mixed in a mixer with 750 grams of a hot 10% solution of phosphoric acid-N-methylstearylamide-diamide in ethanol. After evaporating the solvent at 75 C. the mixture was worked up into granules which were injection-molded into plates. The specific transmission resistivity of the plates obtained was 10 ohms/cm. After the plates had been rubbed with a woolen cloth an attraction of cigarette ash was not observed.

Example 26 In a mixer 75 grams of phosphoric acid-N-methylstearylamide-diarnide molten at 110 C. were introduced through nozzles into 10 kilos of linear (low-pressure) polyethylene powder (density: 0.96 g./cc., specific resistivity l ohms/cm).

After thorough homogenizing the mixture was worked up into granules which were injection-molded into plates. The specific transmission resistivity of the plates obtained Was ohms/cm. After being vigorously rubbed with a woolen cloth the plates did not attract cigarette ash.

Example 27 10 kilos of a branched (high-pressure) polyethylene powder having a density of 0.918 g./cc. and a specific transmission resistivity of 10 ohms/cm. were, as described in Example 14, finish-ed with 150 grams of phosphoric acid-N-methylstearylamide-diamide in order to acquire anti-static properties. The injection-molded plates so obtained had a transmission resistivity of 10 ohms/ cm. After being vigorously rubbed with a woolen cloth the plates did not attract cigarette ash.

Example 28 10 kilos of isotactic polypropylene-power (density: 0.905 g./cc., specific transmission resistivity 10 ohms/ cm.) were, as described in Examples 14, and 16, finished with 75 grams of phosphoric acid-N-methylstearylamide-diamide in order to acquire anti-static properties.

When measured the injection-molded plates obtained according to the three processes exhibited a specific transmission resistivity of '10 ohms/ cm. After being rubbed vigorously with a woolen cloth the plates did not attract cigarette ash.

11 2 Example 29 10 kilos of a linear (low-pressure) copolymer powder composed of of ethylene and 10% of propylene (density: 0.928 g./cm. ball indentation hardness 230/ 205 kg./cm. specific transmission resistivity 10 ohms/ cm.) were, according to Example 14, mixed with 75 grams of phosphoric acid-N-methylstearylamide-diamide and injection-molded into plates.

The injection-molded plates thus obtained had a specific transmission resistivity of 5-10 ohms/ cm. After having been rubbed vigorously with a woolen cloth the plates did not attract cigarette ash.

Example 30 According to Example 16, 75 grams of phosphoric acid- N-methylstearylamide-diamide were applied to 10 kilos of polycarbonate granules (density: 1.2 g./cc., specific transmission resistivity 10 ohms/cm). Before homogenizing the granules on the extruder with subsequent processing in the injection-molding machine, the material thus treated was always carefully dried in a through-dryer at C.

The specific transmission resistivity of the injectionmolded plates thus obtained was 10 ohms/cm. An attraction of cigarette ash was not observed after the plates had been rubbed with a woolen cloth.

Example 3] 10 kilos of a granular product of linear (low-pressure) polyethylene that had, as described in Example 24, been finished with 75 grams of phosphoric acid-N-methylstearylamide-diamide in order to acquire anti-static properties were processed on the extruder into sheets by means of a slot die.

The specific transmission resistivity of the sheets so prepared was 10 ohms/cm. An attraction of cigarette ash was not observed after the plates had been rubbed with a woolen cloth.

Example 32 200 grams of a commercial unsaturated polyester resin obtained by condensation of 5 moles of ethylene glycol with 3 moles of maleic anhydride and 2 moles of phthalic anhydride and final dissolution of the condensation product in 30% by weight of styrene, were cast into plates after the addition of 2% of methylethyl ketone peroxide, 0.1% of cobaltous naphthenate and 0.75% of phosphoric acid N methylstearylamide-diamide and hardened at room temperature with the exclusion of air. After being vigorously rubbed with a woolen cloth the plates did not attract cigarette ash.

Example 33 200 grams of a commercial epoxide resin on the basis of 4,4-diphenylol propane-l-epichlorohydrin having an epoxide equivalent of were mixed with -16 grams of diethylene triamine and 10 grams of a 20% solution of phosphoric acid-N-methylstearylamide-diamide in dibutyl phthalate and the mixture cast into a plate. After 3 hours tempering at 50 C. the mixture of resin and hardener was hardened. After being vigorously rubbed with a woolen cloth the plates did not attract cigarette ash.

Example 34 wherein X is a member selected from the group consisting of oxygen and sulfur, Y is a radical selected from the group consisting of 14 and R R is an alkyl radical of 1-20 carbon atoms, and each R substituent is selected from the group consisting of hydrogen, an alkyl radical of 1-20 carbon atoms, phenyl, and alkylphenyl, said phosphorus amide imparting anti-static properties to the composition.

2. The composition of claim 1 in which the hydrocarbon radicals of the phosphorus compound may be substituted by a radical selected from the group consisting of amino, hydroxy, alkoxy and carboxy-alkyl groups.

3. The composition of claim 1 wherein the phosphorus amide is phosphorus acid-N-methylstearylamide-diamide.

References Cited by the Examiner UNITED STATES PATENTS 2,628,224 2/1953 Cairns et al.

3,134,742 5/1964 Wismeretal 26045.9

FOREIGN PATENTS 584,539 10/1959 Canada.

853,186 11/1960 GreatBritain.

1,091,078 10/1960 Germany.

ALFRED L. LEAVITT, Primary Examiner.

MORRIS LIEBMAN, ALEXANDER H. BRODMER- KEL, Examiners. 

1. A NEW COMPOSITION OF MATTER CONSISTING ESSENTIALLY OF (A) A HIGHER MOLECULAR WEIGHT COMPOUND SELECTED FROM THE GROUP CONSISTING OF POLYSTYRENE, COPOLYMERS OF STYRENE WITH BUTADIENE, COPOLYMERS OF STYRENE WITH ACRYLONITRILE, COPOLYMERS OF STYRENE WITH VINYLCARBAZOLE, POLYVINYL CHLORIDE, VINYL CHLORIDE COPOLYMERS, PLYTEREPHTHALATES, POLYOLEFINS, POLYCARBONATES, POLYCRYLONITRILE, POLYACRYLIC ACID ESTERS, POLYMETHACRYLIC ACID ESTERS, POLYAMIDES, POLYURETHANES, POLYVINYL ESTERS, POLYACETALS, POLYMERS OF FLUOROOLEFINS, CELLULOSE DERIVATIVES, UNSATURATED POLYESTERS, AND EPOXY RESINS, AND (B) 0.1-7% BY WEIGHT, BASE ON THE WEIGHT OF THE HIGH MOLECULAR COMPOUND, OF AT LEAST ONE ORGANIC PHOSPHORUS AMIDE HAVING THE FORMAULE SELECTED FROM THE GROUP CONSISTING OF 